A sudden increase in crater depth was observed during high irradiance (>1010 W/cm2) laser ablation of silicon, and it is attributed to the phenomenon of phase explosion. The threshold irradiance for phase explosion showed a dependence on two laser parameters: laser beam spot size and wavelength. For a larger beam size and longer incident wavelength, a higher laser irradiance was required to generate phase explosion. The rapid increase of crater depth above the phase explosion threshold irradiance correlated with a significant increase in the ICPMS signal intensity. The ratio of crater volume to ICPMS intensity, which represents entrainment efficiency, remained the lowest at laser irradiances slightly above the phase explosion threshold. However, this ratio increased at irradiances well above the threshold (>1011 W/cm2). Chemical analysis using laser ablation at irradiance above 1011 W/cm2 provides increased sensitivity via improved entrainment and transport efficiency and increased ablation rate.